Dyeing wool with fluorine substituted pyrimidine containing azo reactive dyestuff

ABSTRACT

Process for dyeing wool in a dyebath in the acid to neutral range wherein the dyestuff is a reactive dyestuff having the formula   IN WHICH D is the residue of an organic dyestuff, R is hydrogen or a lower alkyl, R1 is hydrogen or a substituent, R2 is hydrogen, halogen, substituted or unsubstituted alkyl, alkenyl, aralkyl, aryl, carboxcyclic acid ester, carboxcyclic acid amide, alkylsulphone, or arylsulphone; and F is fluoro. The dyed wool possesses excellent fastness to wet processing.

United States Patent [1 Bien et al. Oct. 7, 1975 [5 DYElNG WOOL WITH FLUORINE 3,208,990 9/!965 Benz et al, 260/154 x SUBSTITUTED PYRIMIDINE CONTAINING lsiernz e:i al,t .l... c max er e a AZO ACTIVE DYESTUFF 3,463,77l 8/1969 Benz et al, .t 260/l54 x [75] Inventors: Hans-Samuel Bien, Burscheid; Brich Klauke, odemhal-Hahnenbelfli bOlh Primary Examiner-Benjamin R. Padgett f G r y Assislant ExaminerE. A. Miller [73] Assignee: Bayer Aktiengesellschait, Attorney Agen" or Firm Plum[ey & Tyner Leverkusen-Bayerwerk, Germany 22 Filed: Jan. 22, 1973 [57] ABSTRACT I Process for dyeing wool in a dyebath in the acid to [2H Appl' 325700 neutral range wherein the dyestuff is a reactive dye- Related US. Application Data Stuff having the fmmula [60] Continuation of Ser. No. 155,663, June I7, I97], abandoned, which is a division of Ser, No, 664.943, Sept, 1, l967, Pat. No. 3,669,95l. R

o N 1 \N F [30] Foreign Application Priority Data R 2 I 7'- Sept, 10, 1966 Germany 50l8l Mar. 25, I967 Germany 5l942 52] U s C h /41 R; /4 3; 3/43; in which D is the residue of an organic dyestuff, R is 2 0/154 hydrogen or a lower alkyl, R, is hydrogen or a substit- 51 im. (31. D06? 1/02 2 is hydrogen, halogen, substituted or unsubsti- [53 Field f Search 41 B 43 4 2 54 tuted alkyl, alkenyl, aralkyl, aryl, carboxcyclic acid ester, carboxcyclic acid amide, alkylsulphone, or arylsul- 55 References Cited phone; and F is fluoro. The dyed wool possesses excellent fastness to wet processing. 3,l98,782 8/1965 Andrew at al. 260/154 X 6 Claims, N0 Drawings DYEING WOOL WITH FLUORINE SUBSTITUTED PYRIMIDINE CONTAINING AZO REACTIVE DYESTUFF This is a continuation of Ser. No. [55,663 filed June 17, i971, now abandoned, which in turn is a divisional application of Ser. No. 664,943 filed Sept. 1, I967. now US. Pat. No. 3,669,951.

The present invention relates to valuable new reactive dyestuffs of the general constitution I \N D-N I I F l R i "2 N in this formula D denotes the radical of an organic dyestuff, R is hydrogen or a lower alkyl group, R is hydrogen or a substituent, R means hydrogen, halogen. optionally substituted alkyl, alkenyl, aralkyl or aryl radicals or carboxylic acid ester, carboxylic acid amide, alkyl-sulphone and arylsulphone groups, and F is a fluoro substituent.

In the dyestuffs of the general formula (l) the group N(R) is linked directly to a carbon atom of the pyrimidine ring in the 2- or 4-position. On the other side the group N(R) is linked to an aromatic ring of the dyestuff D either directly or via a further bridge member. such as SO or CO, as in the case of amide groupings, or via an alkylene group, an alkylene-CO, an arylcnc, arylene-SO, arylene-CO- or a triazine or diazine ring or an arylcne-amidosulphonyl group. If such further bridge members contain heterocyclic ring systems. as is the case with triazinyl or pyrimidinyl radicals, these too. may contain reactive atoms or groupings, such as halogen atoms or other substituents of which large numbers are known.

Examples of substituents R in the 5-position of the pyrimidine ring are: halogen, such as Cl, Br and F; alkyl radicals, such as -CH;, and -C H substituted alkyl radicals, such as monodior trichloroor tribromomethyl, trifluoromethyl radicals; alkenyl radicals, such as vinyl or halovinyl and allyl radicals; -NO CN, carboxylic acid, carboxylic acid ester and optionally N-substituted carboxylic acid or sulphonic acid amide groups, sulphonic acid and sulphonic acid ester groups, alkyl sulphonyl, aralkylsulphonyl or arylsulphonyl radicals.

Suitable substituents R in the 6-position of the pyrimidine ring are, for example, halogen, such as Cl, Br and F; alkyl, such as methyl and ethyl radicals; alkenyl, such as vinyl, halovinyl and allyl radicals; and substituted alkyl radicals, such as mono-, dior trichloroor -bromo-methyl or trifluoromethyl radicals; carboxylic acid esters, such as the methyl and ethyl esters; carboxylic acid amide groups including the N-substitution products; alkylsulphonyl and arylsulphonyl radicals, such as CH;,SO C H SO C,,H -,SO and p- Cl--C,,H SO

Dyestuffs in which R, and R denote hydrogen, halogen and/or alkyl radicals, belong to a preferred group of the compounds according to the invention.

The raw dyestuffs may contain the radical once or several times in the molecule. Dyestuffs with l to 2 reactive radicals of this type are preferred for economic reasons.

Suitable pyrimidine rings (IIIl bromo4-pyrimidinyl, 2-fluoro-5 bromo-6-methyl-4-pyrimidinyl 2fluoro-5-bromo-6- chloromethyl-4-pyrimidinyl, 2,6-difluoro-5- chloromethyI-4-pyrimidinyl, 2,6-difluoro-5-nitro-4- pyrimidinyl, Z-fluoro-6-methyl-4pyrimidinyl, Z-fluoro- 5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4- pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6- trifluoromethyl-6-chloro-2-fluoro-4-pyrimidinyl, 6- trlfluoromethyl-2-fluoro-4-pyrimidinyl. Z-fluoro-S- nitro-4 -pyrirnidiny|, 2-fluoro-5-trifluoromethyl-4- pyrimidinyl, Z-fluoro-S-methylsulphonyl-4-pyrimidinyl, 2-fluoro-5-phenyl-4-pyrimidinyl, Z-fluoro-S-carbonamido-4-pyrimidinyl, Z-fluoro-5-carbomethoxy-4- pyrimidinyl, 2-fluoro-S-bromo-G-trifluoromethyl-4- pyrimidinyl. 2-fluoro-6-carbonamido4-pyrimidinyl, 2-fluoro-6-earbomethoxy-4-pyrimidinyl, 2-fluoro-6- phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-S-methylsulphonyl-4-pyrimidinyl, 2- fluoro-5-sulphonamido-4pyrimidinyl, 2-fluoro-5- chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5- trifluoromethyl-4-pyrimidinyl.

Among the many possibilities of attaching the radical (ll) to D, the direct linkage of the groups N(R) to a carbon atom of a carbocyclic ring of D is preferred. Suitable bridge members of this or another kind, with the inclusion of the group N(R), are, for example (A standing for the radical of the formula lll); NH-A, N(CH )A, -N(C H )A, N(C H,)A, CONHA, SO NH-A, CON(CH )A, SO N(CH,,)A as well as the corresponding N- ethyland N-propylamides, HNCONHA, HN-CH CONHA, N(CH )CH CON- HA, NHCH CH -NH-AN- HSO (CH NHA, NH--CO-(CH- ,NHA, CH NHCO(CH NH-A,

3 l or 2 NH-A as well as the corresponding N-alkyl( l-5 C)-amides or -amines CH lCH W able, inter alia:

R N w I F l l a 2'; N

1. A dyestuffs in which B and E represent aromatic, carbocyclic or heterocyclic radicals and, in particular, B is the radical of a carbocyclic diazo component of the benzene or naphthalene series and E is the radical of an enolic or phenolic coupling component, e. g.

a S-pyrazolone, S-aminopyrazole, acetoacetic acid arylamide, hydroxynaphthalene or aminonaphthalene; B and E may otherwise contain any substituents customary in azo dyestuffs, including further azo groups; R stands for a CH group or, preferably for a hydrogen atom, and R and R'-;, independently of one another, stand for hydrogen or halogen groups, such as Cl, Br or F.

Especially valuable dyestuffs of this series are those which are water-soluble and, in particular, those which contain sulphonic acid and/or carboxylic acid groups. The azo dyestuffs may be metal-free or metalcontaining, the copper, chromium and cobalt complexes being the preferred metal complexes.

Important azo dyestuffs are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-lphenyl-S-pyrazolone series, the benzene-a20- aminonaphthalene series, the naphthalene-azo-naphthalene-series, the naphthalene-azol -phenylpyrazolone-S series and the stilbene-azo-benzene series, the dyestuffs which contain sulphonic acid groups being again preferred. in the case of metal complex azo dyestuffs, the groups attached to the metal complex are preferably in the o-positions to the 320 group, for example, in the form of o,o-dihydroxy-, o-hydroxy-o'- carboxy-, o-carboxy-o'-aminoand o-hydroxy-o'- aminoazo groupings. Particularly eminent types of monoazo dyestuffs of the kind obtainable according to the invention are illustrated by the following formulae:

}(o) denotes that the stated radicals stand in the adjacent position to each other; A stands for the radical in which R, and R, have the same meaning as above;

or in other words, A stands for a 2-fluoropyrimidine- 4-yl ring containing a radical R in the 5-position and a radical R in the 6-position, or A stands for a 4- fluoropyrimidine-Z-yl ring containing a radical R in the 5-position and a radical R' in the 6-position; acyl stands for an acyl radical, in particular a lower aliphatic carbonyl or sulphonyl residue having 1 to 5 carbon atoms or an aryl carbonyl or aryl sulphonyl residue of the benzene and substituted benzene series; the nuclei drawn with dotted lines indicate that these nuclei may be present or absent. 2. Anthraquinone dyestuffs in which L and L denote substituents. especially sulphonic acid groups, p denotes an integer from 0 to 2, R is a methyl or ethyl group or hydrogen, R, and R independently of one another, are hydrogen or halogen radicals. 3. Phthalocyanine dyestuffs I (ta ll J. R '2 in this formula Po stands for the radical of a nickelor copper-phthalocyanine, L and L are substituents, especially sulphonic acid groups, r denotes an integer from 0 to 2, q is the number 0 or l, R is a methyl group or, preferably, hydrogen, R and R independently of one another, are hydrogen or halogen radicals. The phthalocyanine radical Po preferably carries as further substituents 1-2 sulphonic acid and/or l-2 sulphonic acid amide groups, such as SO RH SO N-alkyl, SO N- (alkyl): and SO NH(aryl) groups, alkyl standing for alkyl radicals with l-3 carbon atoms.

The above compilation of a selection of suitable azo, anthraquinone and azaporphin dyestuffs and of fluorosubstituted pyrimidine rings does not represent a limitation of the general formulae, either with regard to the preparative possibilities of producing such dyestuffs within the scope of the general formula (I), or with regard to the valuable properties of these products in respect of application techniques. The new dyestuffs may otherwise contain any substituents customary in dyestuffs, such as sulphonic acid, carboxylic acid groups; sulphonamide and carbonamide groups which may be further substituted on the nitrogen atom of the amide; sulphonic acid ester and carboxylic acid ester groups; alkyl, aralkyl and aryl radicals; alkylamino, aralkylamino, arylamino, acylamino, nitro and cyano groups; halogen atoms such as Cl, Br and F; hydroxy, alkoxy, thioether azo groupings and the like. The dyestuffs may also contain further groupings capable of fixation, such as monoor dihalo-triazinylamino, mono-, dior trihalopyrimidinylamino, 2,3-dihalo-quinoxaline- (a-carbonyl or -6-sulphonylamino, l ,4-dihalophthalazine-G-carbonylor -6sulphonylamino, Z-haloor 2-alkylsulphonylor 2-arylsulphonylbenzothiazole- S-carbonylor 5-sulphonylamino, alkylsulphonylpyrimidinyl, arylsulphonyl-pyrimidinyl, esterified sulphonic acid hydroxy alkylamide and hydroxy alkylsulphone groups, sulphoflu0ride-, haloalkylamino, acryloylamino, haloacylamino groups or other reactive groups.

The new dyestuffs of the formula (I) are obtained by introducing into dyestuffs or dyestuff intermediates, by known methods at least one fluoro-substituted pyrimi- (lll) linked via an amino group N(R). If dyestuff intermediates are used, these are then converted into the desired final dyestuffs in known manner, particularly by a diazotising, and/or coupling and/or condensing reaction. in the formula (III) R, denotes hydrogen or a substituent and R means hydrogen, halogen, optionally substituted alkyl, all-tenyl, aralkyl or aryl radicals, carboxylic acid ester, carboxylic acid amide, alkylsulphone or an arylsulphone group; F stands for a fluorine atom.

The introduction into dyestuffs or dyestuff intermedi ates. of the radical (lll) via an amino group N(R) can be carried out by various methods of preparation. For example, dyestuffs or dyestuff intermediates which contain amino or amide groups and exhibit a reactive hydrogen atom on the nitrogen atom of the amine or amide, can be reacted with compounds of the general formula i F (xm) R2 N in which R and R have the same meaning as above, F stands for a fluoro substituent and X for a radical which can be split off as an anion, to form dyestuffs of the general formula (I), and, if dyestuff intermediates are used, these can then be converted into the desired final dyestuffs in a suitable manner. Among the reactive substituents X which can be split off as anionic radicals, the fluoro substituent is of particular interest. Other radicals which can be split off as anions and are suitable according to circumstances are, for example quaternary ammonium groups, such as a):; and 2 5):t

Heterocyclic pyrimidine compounds of the formula (Xlll) which are suitable, for the reaction are, for example: 2,4-difluoropyrimidine, 2,4-difluoro-6- methylpyrimidine, 2,6-difluoro-4-methyl-5- chloropyrimidine, 2,4,6-trifluoropyrimidinc, 2,4-

cifluoropyrimidinc-S-ethylsulphone, 2.6-difluoro-4- chloropyrimidine, 2.4.5,fi-tctrafluoropyrimidine, 2,4,6- trifluoro-S-chloropyrimidine, 2,6-difluoro-4-methyl-5- bromopyrimidine, 2,4-difluoro-5,6-dichloroor dibromopyrimidine, 4,6-difluoro-2,S-dichloroor -dibromopyrimidine, 2.6-difluoro-4-bromopyrimidine, 2,- 4,6-trifluoro-S-bromopyrimidine, 2,4,6-trifluoro-S- chloromethylpyrimidine, 2,4,6-trifluoro-5- nitropyrimidine, 2,4,6-trifluoro-5-cyanopyrimidine, 2,- 4,6-trifluoropyrimidine-5-carboxylic acid alkyl esters or -5-carboxylic acid amides, 2,6-difluoro-5-methyl-4- chloropyrimidine, 2,6-difluoro-S-chloropyrimidine, 2,- 4,6-trifluoro-S-mcthylpyrimidine, 2,4,5-trifluoro-6- methylpyrimidine, 2,4-difluoro-5-nitro-6- chloropyrimidine, 2,4-difluoro-S-cyanopyrirnidine, 2, 4-difluoro-S-methylpyrimidine, 6-trifluoromethyl-5- chlro-2,4-difluoro-pyrimidine, 6-phenyl-2,4- difluoropyrimidine, 6-trifluoromethyl-2,4- difluoropyrimidine, -trifluoromethyl-2,4,6- trifluoropyrimidine. 5-trifluoromethyl-2,4- difluoropyrimidine, 2,4-difluoro-5-nitropyrimidine, 2,- 4-difluoro-5-trifluoromethyl-pyrimidine, 2,4-difluoro- 5-methylsulphonylpyrimidine, 2,4-difluoro-5- phcnylpyrimidine, 2,4-difluoro-5-carbonamidopyrimidine, 2,4-difluoro-5-carbomethoxy-pyrimidine, 2,4-difluoro-o-trifluoromethylpyrimidine, 2,4-difluoro- S-bromo-o-trifluoromethylpyrimidine, 2,4-difluoro-ocarbonamido-pyrimidine, 2,4-difluoro-6-carbomethoxy-pyrimidine, 2,4-difluoro-6-phenylpyrimidine, 2,- 4-difluoro-6-cyanopyrimidine, V 2,4,6-trifluoro-5- methylsulphonylpyrimidine, 2,4-difluoro-5-chloro-6- carbomethoxy-pyrimidine, 2,4-difluoro-5- sulphonamido-pyrimidine.,

In the condensation reaction with the dyestuffs or dyestuff intermediates containing amino or amide groups, these pyrimidine derivatives can be assumed to react in the 4-position, the radical X being split off. In the general formulae (I), (ll) and (IV) to (Xll) the pyrimidine ring is therefore presumably and preferably attached via the 4-position to the radical of the dyestuff containing the N(R) or N( R')-group.

The fluoro-pyrimidine compounds mentioned above and others which can be used according to the invention are generally readily obtained by reacting the corresponding chloro or bromo compounds with alkali metal fluorides, for example, with potassium fluoride, NaRF KSO- F, SOF,-,, AgF or by reacting corresponding OH compounds with SP COF COCIF or cyanuric fluoride, or by heating corresponding diazonium tetrafluoroborates. f

Particularly preferred for the reaction according to the invention are those reactive components which correspond to the formula in which R and R independently of one another, denote hydrogen or halogen radicals (Cl, Br or F), and Y is a radical which can be split off as an anion, particularly a fluoro substituent.

The reaction of the dyestufi's or dyestuff intermediates containing amino or amide groups with heterocyclic compounds of the formula (Xlll) is carried out in accordance with the type of starting compounds used in an organic, aqueous-organic or aqueous medium at temperatures of l0 to [00C, preferably at 0 to C, in the presence of alkaline condensation agents, such as aqueous alkali metal carbonate or alkali metal hydroxide solutions.

If dyestuff intermediates are used, the condensation products obtained are converted in usual manner into the desired final dyestuffs. This process is primarily interesting for the preparation of azo dyestuffs in that, for example, a diazo and/or coupling component containing a reactive amino or amide group, is first reacted with the reactive component (Xlll) or (XIV) and the resultant intermediate subsequently converted by diazotisation and/or coupling and/or condensation into an azo dyestuff. In the latter further conversion reactions as are customary in azo dyestuffs can subsequently be carried out, for example, acylating, condensing, reducing and metallising reactions.

Also when preparing other dyestuffs, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (Xlll) or (XIV) (XIV) can first be performed with an intermediate, for example, with m-phenylene-diamine or an m-phenylene-diamine-sulphonic acid, and the reaction product obtained can subsequently be further condensed with an anthraquinonesulphonic acid halide or with a copperor nickel-phthalocyanine-sulphonic acid halide to form a reactive phthalocyanine dyestuff.

Another variant for the preparation of the new dyestuffs of the formula (I) which is applicable in some cases consists that in dyestuffs or, in particular, in dyestuff intermediates which contain at least one group of the general formula I R [(2 NA- in which R, R, and R have the same meaning as above and Z represents a radical which can be split off as anion, with the exception of a fluoro substituent, Z is exchanged in known manner for a fluoro substituem and, if dyestuff intermediates are used, these are subsequently converted into the desired final dyestuffs. The exchange of one or more substituents Z which can be split off as anions, for example, of Clor Br-atoms, for fluoro substituents can be carried out, for example, in the manner already explained.

As has already been mentioned for some cases, the dyestuffs obtainable by the various methods described above can be subjected to further reactions which are customary for dyestuffs in that, for example, metallisable dyestuffs are treated with metal-yielding agents, especially with chromium, cobalt, copper or nickel salts; dyestuffs containing reducible groups, especially nitro groups, are reduced; dyestuffs containing aeylatable groups, especially acylatablc amino groups, are acylated', or dyestuffs are subsequently treated with sulphonating agents, such as chlorosulphonic acid, oleum or SO;,, in chlorinated hydrocarbons, in order to introduce (further) sulphonic acid groups into the products. The last-mentioned process is sometimes of particular importance in the series of anthraquinone and phthalocyanine dyestuffs. Dyestuffs of the formula (I) which contain sulphonic acid and/or carboxylic acid groups are preferred within the scope of the present invention.

Depending upon the number of reactive-HNR- groupings suitable for the conversion reaction which are present in the dyestuff radical or dyestuff intermediates, one or more groupings of the general formula (II) can be incorporated with the dyestuffs, In the majority of cases the number m 4 will not be exceeded, but it is also possible to synthetise dyestuffs, especially those of a higher molecular structure, with more than 4, e.g. with up to 8 groupings of the formula (II).

If the dyestuffs produced according to process contain groups forming metal complexes, these can be converted into their metal complex compounds by the action of metal-yielding agents, for example, of copper, nickel, chromium or cobalt salts. They can also be subjected to other conventional conversion reactions, such as diazotising, coupling acylating and condensing reactions,

The reaction of dyestuffs containing amino groups with reactive components of the formula (XIII) or (XIV) yields groups ofparticularly preferred dyestuffs, if those amino group-containing starting dyestuffs are used, from which the dyestuffs of the formulae (IV) to (XII) are derived, i.e. those containing the grouping N(R')H or N(R)H, instead of the group or the group N( R)A.

In the production of phthalocyanine dyestuffs it is possible to prepare first a diaminoaryl compound which is mono-condensed with the reaction component (XIII) or (XIV) and subsequently to condense this with, preferably, copperor nickel-phthalocyaninesulphonic acid halides; other amino compounds, such ammonia, aliphatic amino compounds and/or aromatic amino compounds may be added simultaneously or subsequently. In this way, there are obtained phthalocyanine-, preferably copperor nickelphthalocyanine-sulphonamide dyestuffs which contain a certain proportion of sulphonarylamide groups carrying the reactive group and, in addition, a certain proportion of non-reactive sulphonamide groups and/or free sulphonic acid groups. Likewise, copper or nickel-phthalocyanine-sulphonic acid-(aminoaryl )-amides which may contain additional, optionally N-substituted sulphonamide groups of different type and free sulphonic acid groups, can be condensed on the amino group of the aminoaryl radical with reactive components (XIII) or (XIV) to form the new dyestuffs (I).

The new dyestuffs are extremely valuable products which are suitable for a great variety of applications. As water-soluble compounds they are primarily of interest for the dyeing of textile materials containing hydroxyl groups and containing nitrogen, especially textile materials of natural and regenerated cellulose, and also of wool, silk, synthetic polyarnide and polyurethane fibres Due to the reactive fluoro substituent or substituents in the pyrimidine ring, the products are particularly well suited as reactive dyestuffs for the dyeing of cellulose materials by the methods which have recently become known for this purpose. The fastness properties obtained, especially the fastness to wet processing, are excellent.

For dyeing cellulose, the dyestuffs are preferably used in an aqueous solution to which compounds of alkaline reaction, such as alkali metal hydroxide or alkali metal carbonate, or compounds which can be converted into substances of alkaline reaction, such as alkali metal bicarbonate, Cl;,C-COONa, can be added. Further auxiliaries may be added to the solution, but these should not react with the dyestuffs in an undesirable manner. Additives of this kind are, for example, surface-active substances, such as alkylsulphates; substances preventing the migration of the dyestuff; dyeing auxiliaries such as urea; or inert thickening agents, such as oil-in-water emulsions, tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to be dyed, for example, by padding on a foulard (short bath) or by printing. followed by heating for some time at an elevated temperature. preferably 40 to l50C. Heating can be carried out in a hot flue, in a steaming apparatus, on heated rollers or by intro ducing the material into heated concentrated salt baths, alone or successively in any sequence.

if a padding liquor or dyebath without alkali is used, the dry material is subsequently passed through a solu tion of alkaline reaction to which common salt or Glaubers salt has been added. The addition of salt prevents the dyestuff from migrating from the fibre.

The material to be dyed can also be previously treated with one of the acid-binding agents mentioned above, subsequently treated with the solution or paste of the dyestuff and finally fixed at an elevated temperature as stated.

For dyeing from a long bath, the material is introduced into an aqueous solution of the dyestuff (liquor ratio 1:5 to 1:40) at room temperature and dyeing is carried out for 40 to 90 minutes, possibly with an increase of temperature up to 90C, preferably 50C, while adding portions of salt, for example, sodium sulphate, and subsequently of alkali, for example, sodium phosphates, sodium carbonate, NaOH or KC H. The chemical reaction between the dyestuff and the fibres taking place during this operation. After chemical fixation, the dyed material is rinsed hot and finally soapcd, whereby unfixed residues of the dyestuff are removed. Dyeings of excellent fastness, especially fastness to wet processing and light, are obtained.

In the so-called cold batch padding process, the subsequent heating of the padded fabric can be saved by storing the fabric at room temperature for some time, for example 2 to 20 hours. In this process there is used a stronger alkali than in the dyeing process from a long bath described above.

For printing materials containing hydroxyl groups, there is used a printing paste consisting of the dyestuff solution. a thickening agent, such as sodium alginate, and a compound of alkaline reaction or splitting off alkali upon heating, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium or potassium hydrogen carbonate, and the printed material is rinsed and soaped.

If the dyestuffs contain groupings forming metal complexes, the fastness properties of the dyeings and prints can frequently be improved by an aftertreatment with metal-yielding agents, such as copper salts, for example, copper sulphate, chromium. cobalt or nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

Textile materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibres, are generally dyed by the dyeing methods customarily used for this purpose in the acid to neutral range, a final increase of the pH value of the dye bath, for example, to pH 6.5 to pH 8.5, being sometimes of advantage.

For example, the dyestuffs are applied to synthetic polyamide fabrics as solutions or. preferably. in dispersed form and subsequently after-treated, optionally together with (preferably smaller amounts) of acidbinding agents. such as sodium carbonate. Particularly advantageous results are achieved with those dyestuffs which are insoluble or only sparingly soluble in water. These are worked up by usual methods and with the addition of the known auxiliaries to form a dyestuff ispersion and are applied in this form in the dye bath and/or padding liquor or in a printing paste. Auxiliaries suitable for this application are, inter alia. compounds which prevent the migration of the dyestuff on the fibre, such as cellulose ethers, alkali metal chlorides and sulphates; wetting agents, such as condensation products from ethylene oxide and fatty alcohols or phenols, sulphonated fatty alcohols; solvents, such as thiodiglycol; and also thickening agents, such as starch, tragacanth, alginate thickening, gum arabic etc.

The after-treatment of .the dyeings, impregnations and prints obtained on fabrics of polyamide fibres is preferably carried out at a temperature of 50 to l 10C for 5 to minutes. In the case where the dyestuffs used contain groupings forming metal complexes, the fastness properties of the dyeings can again sometimes be improved with metal-yielding agents, such as copper salts, for example, copper sulphate, or chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

The dyeings which can be obtained with the new dyestuffs are generally characterised by good to very good fastness properties, especially by excellent fastness to wet processing.

Compared with the constitutionally most closely related known reactive dyestufis containing ehloroor bromopyrimidinylamino groups, as are described, for example, in Belgian Pat. Nos. 572,973; 573,299 and 578,742, the new products of the formula (I) have essential advantages with regard to application techniques. In comparison with the most closely related trichloropyrimidinyl dyestuffs, for example, the new dyestufis which contain a 2,6-difluoro-5-chloropyrimidinylamino or a 2-fluoro-5,6- dichloropyrimidinylamino radical, surprisingly, give a better dyestuff yield on cotton and regenerated fibres and are superior with regard to colour depth when dyed from a long bath. in contrast to the known chloropyrimidine reactive dyestuffs, the new fluoropyrimidine reactive dyestufis are also well suited for the socalled cold batch padding process for cotton and regenerated fibres. in the printing process the new dyestuffs can be used for rapid fixation. The bond between the fibre and the dyestuffs in an alkaline medium is frequently stronger than with the known dyestuffs.

The new fluoropyrimidine reactive dyestuffs are also superior to the known chloropyrimidine dyestuffs in that they yield valuable dyeings of good fastness to washing, milling and potting on wool. Dyeings which are fast to wet processing can also be obtained on silk and synthetic superpolyamide and -polyurethane fibres.

In the following Examples the parts are parts by weight, unless otherwise stated.

EXAMPLE I To a solution of 34.7 parts of the sodium salt of 2- aminonaphthalene-4,8-disulphonic acid and 7 parts sodium nitrite in 300 parts of water there are added 28 parts by volume of concentrated hydrochloric acid, while cooling with ice, and the mixture is stirred at 0l0C for one-half hour. After removing the excess nitrous acid. l0.7 parts 3-amino-toluene dissolved in l0 parts of concentrated hydrochloric acid and parts of water are added and the coupling is completed by neutralising the mixture to pH 35. The resultant aminoazo dyestuff is salted out, filtered off with suction, washed and then redissolved at pH 7 to 140 parts of water and 200 parts acetone with the addition of a sodium hydroxide solution. l9.2 Parts 2,4,6-trifluoro- S-chloro-pyrimidine are added dropwise to this solu- A pH of 6-65 is maintained during the condensation by the addition of a sodium carbonate solution. When the reaction is completed, the dyestuff is salted out and isolated. When dried, the dyestuff is a dark powder tion at 2030C and a pH of 5.5-6 is maintained by 5 which dissolves in water to give a blue colour. means of a 2N sodium carbonate solution, Wh th 100 Parts by weight of a cotton fabric are treated on reaction is completed. the resultant dyestuff of the prcthe foulard at room temperature with an aqueous solusumable formula tion containing 2 percent of the dyestutf, l5 g/litre of sodium hydrogen carbonate and 150 g/litre of urea, 3 F m subjected to intermediate crying, heated at 140C for 2 minutes, then rinsed and soaped at the boil. The fabric is dyed in very clear blue shades fast to wet processoo 9 I c 3 c1 F 03 5 EXAMPLE 3 46 Parts of the monoazo dyestuff obtained in analogy is salted out with 210 parts of a saturated sodium chlowith Example 1 y Coupling diazofised ride solution, the product which crystallises in the form aminonaphthalenc'4'8di5ulphonic acid with of yellow needles is filtered off with suction, washed mcthylaminotoluene are dissolved at in 400 with a 2 percent sodium chloride solution and dried in pans of water and 100 Parts acetone and 20 Parts a vacuum at 6-trifluoro-5-chloropyrimidine are added dropwise when a cellulose fabric is printed with a printing while malnminlng 3 P of means of a 2N Sodium paste Which contains, per kilogram 15 g of the carbonate solution; the condensation is continued until stuff, l00 g urea, 300 ml of water. 500 g of alginate Sample no longer exhibits a Change of Colour when thickening (69 g sodium algimnc per kg f thickening) acidified. The resultant dyestuff which has the presumand 2t) g sodium carbonate, and which has been made able formula up with water to l kilogram, the fabric is then dried, 5 CH F steamed at 105C for 1 minute, rinsed with hot water I and soaped at the boil, an intense reddish yellow print ="-N- A N of good fastness to washing and light is obtained.

CH C] F EXAMPLE 2 $0 M 0.] mole of the copper complex compound of the is salted out, filtered off with suction, washed and dried formula at 30C in a vacuum.

A cotton fabric is impregnated with a solution at 20-25C, which contains, per litre of liquor, 20 g of No3s so No the above dyestuff and 0.5 g of a non-ionic wetting 3 agent (c.g. a polyhydroxyethylated oleyl alcohol) as "H2 well as ISO g urea and 15 g sodium bicarbonate. The 40 fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100 percent. "c035 cu Q 3" After an intermediate drying at 5060C. the fabric is heated at 140C for 2 minutes, the dyeing so obtained is thoroughly rinsed with hot water and treated at the prepared according to the instructions of German Pat. 45 boil for 20 minutes with a solution containing, per litre. Specification No. l,l 17.235 by coupling diazotised l- 5 g of Marseilles soap and 2 g sodium carbonate. After amino-8-( benzcne-sulphonyloxy)-naphthalenerinsing and drying, there is obtained an intense reddish disulphonic acid-(3,6) in a soda-alkaline medium with yellow dyeing of good fastness to wet processing, rubthe equivalent amount of 2-acetylamino-5- so bing and light. hydroxynaphthalcne-disulphonic acid-(4,8), converin the following Table there are listed the diazo comsion of the monoazo compound into the copper components, coupling components and reactive compoplex by oxidative coppering, and hydrolysis of the acenents linkable to the amino group, from which dyetyl and benzene-sulphonyl groups) are dissolved at pH stuffs can be synthetised in analogy with the instruc- 6-6.5 in 2500 parts by volume of water at 60-65C and tions given in Example l-3, the shades obtained by mixed at 20-30C with 0.12 mols 2,4,6-trifluoro-5- one of the methods of application described above chloropyrimidinc. being likewise stated in the Table.

Abbreviations for the reactive A 2,4.6-trifluoro-S-chloropyrimidine components:

B 2.4,6-trilluoropyrimidine Example Diazo Coupling Reactive Shade No. component component component 4 Z-aminonaphthalenel-amino- Z-mcthoxy- A yellow 6 l-aminonaphthalene- 3,6-disulphonic acid ,v B-disulphonic acid S-methylhenzcne l-amino-3-methyl- Continued Abbreviations for the reactive components:

= 2AA:-trilluoropyrimidinc Example Diaro Coupling Reactive Shade Nu. colnpnnclll component component It 2 -aminonaphthalenel-amino-3-mcthyl- A 5.7-disulphonic acid benzene 9 B l U 2-aminonaphthalencl -amino 3-methyl A 6,8-disulphonic acid benzene I. H B H 12 4-aminoazohenzenel -amino-3 methyl- A brown- 3.4'-disulphonic acid benzene yellow 1 3 l-aminobenzenc-4-sull-aminoJ-methyl- B brownphonic acid 1- benzene yellow aminonaphthalene-osulphunic acid l4 2% 3-sulpho-4'- A yellow aminophenyl )-hmethylbenzothiazolcJ-sulphonic acid l5 Z-aminonaphthalenw l-methylamino-B- 4 8-disulphonlc acid methoxybenzcnc If, l-umino-S-acetyb aminohenzene l7 aniline A 25 EXAMPLE 18 When a fabric of cotton or regenerated cellulose is To a solution of 36.5 parts of the sodium salt of lamino-S-hydroxynaphthalene-3,o-disulphonic acid in 200 parts ofwatcr there are added dropwise at 8-l0C 20 parts 2 4.6-trifluoro-S-chloropyrimidine, and a pH of 5.56 is maintained by continuous neutralisation of the liberated hydrogen fluoride. The reaction is observed by chromatography. The resultant solution of the dyestutf intermediate is poured into 900 parts of water and coupled at a pH of 7-8 and at 0-5C with 17.5 parts of diazotised Z-aminobenzene-sulphonic acid dissolved in 200 parts of water. The product is salted out at a final pH of 6.5 with 80 parts sodium chloride. filtered offwith suction and washed with a 10 percent sodium chloride solution. Drying is carried out in a vacuum at 30-40C.

The dyestuff dyed or printed with this dyestuff according to one of the processes described in Example 1-3. clear bluish red dyeings and prints of good fastness to wet processing, rubbing and light are obtained.

Equally good results are obtained by the following method:

50 g of a cotton skein are dyed in 1 litre of a dyebath containing l.5 g of the above dyestuff by adding 50 g sodium chloride in several portions at to C within 30 minutes, subsequently adding 20 g sodium carbonate and treating the material at the same temperature for 60 minutes. After rinsing, soaping at the boil and drying, a bluish red dyeing of good fastness to wet processing, rubbing and light is obtained.

In the following Table there are listed the shades of further dyestuffs which are synthetised from the likewise specified diazo components, coupling components aminol'ienrcne-fisulphunic acid F and reactive components lmkable to the amino group s 08 H N in the latter, in analogy with the instructions given in Example 18 or also by reacting the corresponding 61 F aminoazo dyestuff with the reactive components, and which can be dyed or printed on to cellulose materials H955 by one of the methods described above;

50 Abbreviations for reactive components as in Table of forms red small needles. Example 3.

Example Diazo Coupling Reactive Shade NU. component component component 1) l -aminohenzcne- 2 l-amino-S-hydroxy- B red sulphonic acid naphthalene-3.6- disulphonic acid 20 aminobenzcnc l-( 3 -aminobenzene' A amino)-8-hydroxynaphthalene-3.6- disulphonic acid n B n 22 l -amino-2-carboxyl-amino-8-hydroxy- A benIenc-4-sulphonic naphthalene-3.5 acid disulphonic acid 23 l-amino-4-methyl- A henlene-l-sulphonic acid 24 I -aminu- 3-acetyl- B Continued Example Diazo Coupling Reactive Shade No. component component component 25 lamino-3-(2'-[4"- A sulphophcnylamino l-4' chlorotriazinel ',3'. 5 '-yl-o' Laminobenzene o-sulphonic acid 26 l-aminohenzenc-l Z-amino-S-hydroxy- A orange sulphonic acid naphthalene7- sulphonic acid 26a l-amino3-( 2 4 Z-amino-5hyt|roxy A orange sulphophenylamino1- naphthalenc-7- 4-meth vlaminosulphonic acid triazinel 'tIl.5-yl- 6' )-aminobenzene-6- sulphonic acid 27 l -aminohenzene- 2-mcthylamino-5- A orange 2-sulphonic acid hydroxy-naphthalene- 7sulphonic acid 28 lamino-4-acetyl- A scarlet amino-fi-sulphonic acid 29 Z-amino-fihydroxy- A naphthalene-7- sulphonic acid S Na \ HO llH-OC-C H -ll =N EXAMPLE 30 P To a solution of 21 parts of the sodium salt of l,3- M m1 diaminobenzene-fi-sulphonic acid in l()() parts of water "e0 8 5 there are added with good stirring 200 parts 2,4.6-tri- P 01 q l I fluoro chloropy rimidlnc ind the mixture is stirred at 30 which is salted out, mtered Off with mono". washed 2U3()C. while continuously neutralising the liberated hydrofluoric acid to pH 67, until a sample which is diazotised and coupled with l-hydroxynaphthalenelsulphonic acid yields a clear yellowish red coloration. The resultant dyestuff intermediate is directly diazotised, after the addition of ice; with 7 parts sodium nitrite and 28 parts of concentrated hydrochloric acid and subsequently combined with a previously prepared solution of 47 parts of the sodium salt of benzoylamino-8-hydroxynaphthalcne-3,6-disulphonic acid and 12 parts sodium carbonate in 200 parts of water, whereby coupling takes place to give the dyestuff of the formula and dried at 30-40C in a vacuum. The dyestuff readily dissolves in water to give a red colour and yields on cellulose materials by one of the processes described above clear bluish red dyeings and prints.

In the following Table there are listed the shades and the ph value of the coupling medium of dyestuffs which are prepared in analogy with the instructions of Example 30 from a diazo component containing a further, preferably acylatable amino group, from a coupling component and from a reactive component linkable with the diazo component. The methods described above can be used for dyeing and printing cellulose materials with the dyestuffs of the Table.

Abbreviations for reactive components as in Table of Example 3 Example Diazo Coupling Reactive pH of No. component component componcoupling Shade ent medium 31 l.3-diaminohcn- 2-aminonaphthalenc- A 4-5 orange zcne-4sulphonic 5.7disulphonic aeid acid 32 2-aminonaphthalene- A 4-5 3.6-disulphonic acid 33 Z-aminonaphthalene- 4-5 b-sulphonic acid 34 l .3 diaminohen- Z-N-methylamino- A 4-5 orange zcne4-sulphonic X-hydroxynaphthak acid eneh-sulphonic acid 35 I 3 '.5'dichloro- A 7-8 red l.2'-thiazole-4- carbonamidoHlhydroxynaphthalene- 3,6-disulphonic acid 30 l-l 2.4'-tlihydroxy- B 7-3 triazine-l '.3'.5'. yl h arnino l-K-hydroxynaphthalene- 3.6-tlisulphonic acid Continued Example Dialo Coupling Reactive pH of No. component component componcoupling Shade em medium 7 l[3'i5' dichlorn- A 7-8 I "Z'JhiKMUlU-V- carhunamidu )-8-hytlroxynaphthalene- 3.64lisulphonic acid 3 8 Z-hydros naphthal- A 8 scarlet cne-lfi-disulphonic acid 39 l -acetylami|10-8- B 7-8 red hydroxynaphthalene- 3 6-disulphonic acid 40 l( 3 '-sulphophenyl 3-mcthyl-pyrazoL A 6 yellow one-5 -l-l l-( 2'5 '-dichloro 6 yellow 4'-sulphophcnyl 3-methyl-pyrazolonc- 5 42 l-(5'.7'-disulpho A 6 yellow naphthyl-Z'JJ- methylpyrazolonc-5 43 l-( 3'-sulphophenyl A 6 yellow 3-methyl-5-aminopyrazole 44 l .4-diaminohcn- 2-amino-8-hydroxynaph- 2cnc-3-sulpl1onic thalcne-6-sulphonic 4-45 red acid 4-5 I .4-diaminohenzenc- Z-acetylamino- A 6-7 scarlet 3-sulphonic acid S-hydroxynaphthalene-7- sulphonic acid 46 l -acetylamino B 6-7 red 5-hydroxynaphthalene7- sulphonic acid EXAMPLE 47 cu 5 l ,6 Parts of the dyestuff of the formula 35 F O Bu O N- N =8 NOD 5 N H l N Cl F "80 m is salted out. pressed off, washed and dried in a vacuum 30:, 38 2 40 at 3040C. Fabrics of cellulose materials can be dyed or printed with this dyestufi' by one of the methods deobtained by diazotisation of l-hydroxy-Z- scribed above in ruby shades fast to wet processing,

rubbing and light.

in the following Table there are listed the heavy metal complexes of further aminoazo dyestuffs and the reactive components linkablc to the amino group, as well as the shades of these dyestuffs on cellulose mate rials The preparation of the aminoazo dyestuffs and their metal complexes and the reaction thereof with the reactive components can be carried out in analogy with the instructions of Example 47.

Abbreviations for reactive components as in Table of Example 3 Example Nov A m inoazo dyestuff Reactive component Shade Complex linked heavy metal l-hydroxy-2-aminohenzene- Cu A ruby 4 6-disulphonic acid --0 2amino 5 -hydroxynaphthalene-7-sulphonic ac id 49 l-hytlroxy-2-aminobenzene- Cu A ruby 4-sulpl1onic acid -b l ethylamino-ihydtoxy naphthalene-7-sulphnnic acid amim -5-hydroxynaphlhuL cncJ-sulphonic acid l-amino-Z-hyd roxy-hnitro-naplithalenc-4- snlphunic acid *9 lclic-Tsulplinnic acid ruhy greenish Continued Example Alumna/.0 Complex Reactive No. dyestulT linked component heavy metal 52 l-amino-2hydroxy-6- Co B reddish nitronaphthalcncJ- black sulphonic acid aminoK-hydroxynaphlhalcnc-J-sulphonic acid 3 l -amino 2-hyilroxy-5- Cu A violet mcthylsulphonyl-henzene -o I-amino 8-hydroxynaphthalene-3.6-disuI- phonic acid 54 Co A grey S5 Cr A greenish black 56 l amino-Z-methylhenzenc-4- Cu blue sulphonic acid lamino-Z-hydrnxy-S-methylhcnrene -v l-amino-K- h droxynuphthalcnc-4 6-disulphonic acid 57 Co B grey 58 Cr A greenish black 5Q 1-amino-2-chlorohcnzene-4- (u A navy blue sulphonic acid l-hydroxy- 2 -acet \l:iminohenzcne hydrolysed. l-amino-S- hydroxynaphthalcne-3 6-disulphonic acid 60 Co A grey (\l l -umino8h droxynaphthal- Co A black ene-4-sulphonic acid el-hydroxy-2 .6-diaminohen- Zenc-4-sulphonic acid l 3-dihydro\ybenzenc 62 l -aminoi-hydroxynaphthalene- Co A black 3,6-disulphonic acid b- I hydro -2.fi-diuminohcnzene- 4-sulphonic acid 2- hydroxynaphthalene 63 l -amino-S-hydroxynaphthal- Co A black 4-sulphonic acid lhydroxy-Z.o-diaminohenzene- 4-sulphonic acid 3' methyIpyrazolone-( 3) EXAMPLE 64 F N 96 Parts (referred to 100% goods) of the copper- NH I phthalocyanine tetrasulphochloride freshly prepared in (so u n the usual manner by the reaction of chlorosulphonic h Cl F Cuthclocyumne acid and thionyl chloride with copper-phthaloeyanme. (so or of the isomeric copper-phthalocyanine tetrasulpho- 2 4-n chloride synthetised from l-sulphobenzcne-3A- M 2-3 diearboxylic acid via the corresponding copperphthalocyanine-tetrasulphonic acid, are suspended in the form of the moist, thoroughly washed filter cake in 500 parts of water and 500 parts of ice, a solution of 50 parts lfiflhminobenzenc in 500 parts of water is so obtained in salted out, washed and dried at 30-40C added and the P i y means of Sodium in a vacuum. It is a dark-blue powder which dissolves carbonate. The suspension is stirred at room temperais i water {0 i a bl colour d d cotton d ture for 24 hours and the pH is constantly maintained generated ll l b one f h d i or imi at 8.5 by the continuous addition of sodium carbonate. processes d ib d above i l bi h d f d The resultant condensation product is precipitated at f m to wet processing. bbi d li ht pH l-2 thC addition Of sodium ChlOfld filtered Off Instead of the part5 coppepphthalocyanine tetwith suction, washed and then redissolved neutral in l h hl i there may b used in u process [000 parts of water. 57 Parts 2,4,6-trifluoro-5- chloropyrimidine are introduced into the blue solution with intense stirring. and the mixture is stirred at 20 -30C, while continuously neutralising to pH 6 by means of a sodium carbonate solution until free amino groups can no longer be detected, The reactive dyestuff of the formula which is otherwise the same as in Example 64-87 parts (referred to percent goods) of the copperor nickel-phthalocyanine trisulphochloride obtained by the reaction of ehlorosulphonic acid with copperor nickel-phthalocyaninc in the form of the moist filter cake thoroughly washed with ice-water; reactive dyestuffs dyeing in clear blue shades are then likewise obtained By working as described in Example 64. but starting from 87 parts copper'phthalocyanine trisulphochloride and replacing the 50 parts of the sodium salt of [,3- diaminobenzene-4-sulphonic acid with 90 parts of the sodium salt of 4.4'-diaminodiphenyl-2,2'-disulphonic acid or 90 parts of the sodium salt of 4.4'-diaminostilbene-2,2'-disulphonic acid, there are likewise obtained reactive dyestuffs which dye cellulose materials by one of the methods described above in clear blue shades fast to wet processing. rubbing and light.

If 4',4",4",4-tetraphenyl-Cu-phthalocyaninc is used as starting material, there is obtained. after sulphochlorination. reaction with l,3-phenylene-diamine and acylation with 2,4.6-trifluoro-5-chloropyrimidine. a reactive dyestuff which dyes cellulose materials in the presence of acid-binding agents in clear green shades fast to wet processing and light.

EXAMPLE (:5

63 Parts l-amino-4-( 4'-aminophenyl )-aminoanthraquinone-2,5,8-trisulphonic acid are dissolved in 630 parts of water, the solution is adjusted to pH 6 by means of a sodium hydroxide solution, 18 parts 2,4,6- trifluoro-S-chloropyrimidinc are then added dropwise at -5C and a pH of 66.5 is maintained by means of a sodium carbonate solution. When the reaction is completed, 7 parts potassium chloride are added. the product is filtered off with suction and washed with a 3 percent potassium chloride solution. The dyestuff which is obtained in the form of blue-green needles is dried in a vacuum at 3040C. lt presumably has the formula H0 0 MH H0 5 O NH NH N and dyes cotton in greenish blue shades.

EXAMPLE 66 if the procedure described in Example 47 is followed but. instead of the copper-containing amino-monoazo dycstuff there used. the equivalent amount of the chromium complex of the aminoazo dyestuff obtained by coupling diazotised l-amino-l-hydroxy-3- chlorobenzene-S-sulphonic acid with l-[3'-(3"- aminophenyl )]-sulphonylimido-sulphonyl-phenyl-3- methyl-pyrazolone-(S) is used as starting material, then a reactive dyestuff is obtained, which dyes cellulose materials by one of the methods described above in yellow-brown shades of good fastness to wet processing. rubbing and light.

EXA MPLE 67 0.1 Mole of the copper complex compound CH -N:N 3

503m: H035 O-(Iu ---o is dissohed in 3000 parts by \olume of water at pH 6 and combined at a temperature of Z0--30C, while stirring, with I68 parts by weight (0.l mole) Z.4.6-trilluoro-S-chloropyrimidine. a pH of 6 being maintained by means of a 2N potassium carbonate solution. The mixture is stirred until the condensation is completed, the dyestuff is separated by the addition of a little sodium chloride and isolated. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained, which dissolves in water to give a green colour and dyes cotton by the methods described in Examples 1-3 in green shades.

A cotton fabric is impregnated with a solution at 25C containing, per litre, g of the above dyestuff and 0.5 g of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol), I g urea and 20 g sodium carbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about percent. After an intermediate drying at 5060C, the fabric is heated at C for 2 minutes, the dyeing so obtained is thoroughly rinsed with hot water and treated for 20 minutes at the boil with a solution containing, per litre, 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, there is obtained a green dyeing of good fastness to wet processing. rubbing and light.

Clear green shades of good fastness properties are also obtained on materials of cellulose by one of the other dyeing or printing methods described in Examples l to 3, l8 and 30.

EXAMPLE 68 ().l Mole of the paste of the aminoazo compound of the formula so r: n n

it it 3 0- cu-o s0 which is obtained by coupling the diazonium compounds of 6-acetamin0-2-aminonaphthalene-4,8- disulphonic acid with 2-hydroxy-naphthalene-3,6- disulphonic acid, hydrolysis and conversion of the monoazo compound into the copper complex, is dissolved in 2000 parts by volume of water at pH 6.5 and combined with 20 parts by weight 2,4,6-triflu0ro-5- chloropyrimidine. The reaction mixture is stirred at 20-30C until the condensation is completed, the pH of the reaction solution being maintained at 6-7 by the addition of a sodium carbonate solution. When the reaction is completed. the dyestuff is salted out, isolated and dried in a vacuum.

The dried dyestuff is a dark powder which dissolves in water to give a violet colour and dyes cotton in the presence of alkali in bluish violet shades.

EXAMPLE 69 An aqueous solution of 0.1 Mole of the copper complex of the formula s 0u- O Parts sodium bicarbonate are then added and a N H diazo suspension from 34 parts of the disodium salt of 2amino-naphthalene-l,7-disulphonic acid in 200 parts of water is added dropwise at 20C within 15 minutes. B2 5 The orange-coloured reactive dyestuff of the formula 3 5 so nq OH prepared according to the instructions of German Pat. 3 N N Specification No. l,()6l ,460 or l,()85,988, is reacted in F the usual manner with 22 parts by weight 2,4,6-trito N N fluoro-S-chloropyrimidine. A pH of 6-7 is maintained 3 I by the addition of sodium carbonate and when the re- CH3 C] F action is completed, the dyestuff is isolated by salting out. in the dry state the dyestuffis a dark powder which which is imn'iediately formed, is completely separated dissolves in water to give a violet colour. Cotton fabric l5 after further stirring for one hour, by means of 80 parts is dyed in violet shades fast to light and wet processing. sodium chloride. filtered off. washed with a dilute so E M E dium chloride solution and dried at 35C in a vacuum The dyestuff dyes cellulose materials by the methods 27.5 Parts of the sodium salt of 2methylamino-5- described above in reddish orange shades of very good hydroxy-naphthalene-7-sulphonic acid are dissolved in 20 fastness to wet processing and good fastness to chlolSU parts of water, 20 parts 2 4.6-trifluoro5 rine. chloropyrimidine are added and the mixture is stirred Orange to red reactive dyestuffs are obtained in an at 30C. while continuously neutralising the hydrogen analogous manner by acylating the aminonaphtholfluoride formed to pH 6-7 by means of a total of 34 sulphonic acids stated in Column 3 of the following parts by volume of a 16 percent sodium carbonate solu- 5 Table with 2,4 6-trifluoro-S-chloropyrimidine and coution After a short time, the aeylation is completed, the pling the resultant acylamino-naphthosulphonic acids pH is 6 and changes no more. with the diazo components stated in Column 2.

Example Diazo Aminonaphthol- Shade on No. component sulphonic acid cotton 7 I 2-aminonaphthalene- 2-ethylamino--hydroxyorange l,7-disulphonic acid naphthalene-Lsulphonic acid 72 2-( fi-hydroxyethylamino orange S-hydroxynaphthalene-7- sulphonic acid 73 2-arnino S-hydroxynaphorange thalene-7-sulphonic acid 74 Z-amino-S-hydroxynaphorange thalenel ,7-disulphonic acid 75 2-amino-8-hydroxynaphscarlet thalene6-sulphonic acid 76 Z-amino-8hydroxynaphscarlet thalene-Bb-disulphonic acid 77 l-aminonaphthalenc- Z-methylamino-S-hydroxyorange 1 .S-disulphonic acid naphthalene-7sulphonic acid 78 Z-ethylamino-5-hydroxyorange nziphthalcne-7-sulphonic acid 79 2-( fi-hydroxyethylamino orange 5-hydroxynin-ihthalene-7 sulphonic acid 80 2-aminoS-hydroxynaphthw orange lene-7-sulphonie acid 8 I lamino-S-hydroxynaphtha orange lenel 7-disul'phonic acid 8 2 Lamino-tl-hydroxyimphthascarlet lene-b-sulphonic acid 83 Z-amino-B-hydroxynaphthascarlet lcne-Il fi-disulphonic acid 84 2-amionaphthalene- Z-amino-S-hydroxynaphthaorange l 5.7-trisulphonic lene7-sulphonie acid acid 85 2-methylamino-5-hydroxyorange naphthalcne-lsulphonie acid 86 Z-aminonaphthalene- Z-amino-R-hydroxynaphthw scarlet I.S 7trisulphonic lene-(v-sulphonic acid acid 8'! 1-aminobcnlene-sul- Z'methyI-aminci-S-hydroxyorange phonic acid naphthalene-7-sulphonic acid 88 Z-lp-h droxyethylamino)- orange S-hydroxynaphthalcne-7- sulphonic acid 8) Z-aminoR-hydroxynaphthascarlet lene-fi-sulphonic acid Continued Example Diazo Aminonaphthol- Shade on No. component sulphonic acid cotton 90 I-amino-H-hydroxynaphthascarlet lene-lh-disulphonic acid 91 Z-an\ino-5-hydroxynaphthaorange lene l .7-disulphonic acid 92 2 aniinonaphthalenel-amino8-hydroxynaphthabluish l--ulphonic acid le|1e-3 fi-disulphonic acid red 93 l-amino-ti-hydrox naphtha bluish lene-kmdisulphonic acid red 94 2 aniinonaphthalenel -aminwS-hydroxynaphthabluish LS-disulphonic acid lone-3.6-disulphonie acid red 95 l -amino-S-hydroxynaphthabluish lene-4.6-disulphnic acid red 96 l -amino-S-hydroxynaphthabluish lcnc-b-sulphonic acid red 97 l-aminonaphthalenel-amino-8-hydroxynaphtha' bluish l.7disulphonic acid lene-lodisulphonic acid red 98 l -amino-8-hydroxynaphthabluish lene-4.6-disulphonic acid red 99 l-amino8-hydroxynaphthabluish lene-b-sulphonic acid red IOU 2-aminonaphthalenel-amino-8-hydroxynaphthabluish l 5,7-trisulphonic lene-b-sulphonic acid red acid I0 I l -amino-4-chlorobenl -an1ino-8-hydroxynaphtha bluish zene-Z-sulphonic acid lene-3.6-disulphonic acid red 1 02 l -amino-2-methoxyl-amino-8-hydroxynaphthabluish benzene-S-sulphonic lone-3.6-disulphonic acid red acid I03 l -amino-benzene-2 l-amino-S-hydroxynaphthabluish carboxylic acid-4 lenc-Ii,6-disulphonic red sulphonic acid acid 104 l -amino-4-acetylviolet aminobenzene-Z- sulphonic acid I l-am ino8-hydroxynaphtha bluish lone-4.6-disulphonic red acid EXAMPLE 106 P N N KM 30 N8 5 5s IIIO S is salted out, filtered off. redissolved in 4000 parts of water at 30C. filtered and separated from the filtrate in completely pure form by the addition of 400 parts sodium chloride. The dyestuft' is dried as usual at 35C in a vacuum. lt dyes cellulose materials by one of the methods described abme in fast yellowish orange shades.

EXAMPLE I07 A neutral solution of 60 parts of the trisodium salt of the aminoazo dyestuff obtained by coupling diazotised 2-aminonaphthalene-3,6,8-trisulphonic acid with 3- acetylaminoaniline in an acetic acid medium, in 500 parts of water is admixed with 20 parts 2,4,6-trifluoro- S-chloropyrimidine and the mixture is stirred at 30C for l hour, a pH of 6 being maintained by the continuous addition of a sodium hydroxide solution. The acylation product which is partially precipitated is completely separated at pH 7 by the addition of I00 parts sodium chloride and filtered ofi. For purification, the reactive dyestuff so obtained can be redissolved in 2500 parts of water at 30C, clarified and separated again by salting out the filtrate with 350 parts sodium chloride. The dyestuff has the formula EH-OOOH 1 F I ll mo s 50 th sponding amounts of the aminoazo dyestuffs obtained from the amino compounds stated in Column 2 and the coupling components stated in Column 3 in the usual manner by diazotisalion and coupling in an acetic acid acylating with 2.4.6tril'luoro5- Fast yellow shades are also obtained on wool and polyamidc fibres Similar dyestuffs are obtained by following the procedure described above but replacing the 60 parts of the sodium salt of 4'-amino-2'-acctylumino-phcnyl-( I medium. and

azonaphthalenc-(Z)-3.6,8-trisulph0nic acid with eorrechloropyrimidine.

Example Diazo Coupling Shade on No. component component eonon I08 2-aminonaphlhalcnc I -amino3-mcthyl-bstrongly l ,5 -disulphonic methoxy-benzene reddish acid yellow l -an1ino- 3-mcthylbcnzene yellow I ll] I-aminonaphlhaleneoreddish sulphonic acid yellow I l I I-umino-3-acctylziminohenzenu I I2 3-aminophenyl-urea I I3 I-amino 3-hydroxyacelylaminobenzene I I4 Z-amin0naphlhalen l-amino 3-mcthyl6- strongly 5,7-disulphonic methoxy-benzenc reddish acid yellow I I5 I-aminonuphthaIene-7- reddish sulphonic acid yellow I I6 l-amino-3-acctylaminobenzene I I7 3-aminophcnyl-urea I [8 I-umino-Il-hydroxyacelylamlnobenzene I I9 I-aminonaphthulcnclumino-3-mcthyl-6- strongly 3.7-disulphonic methoxybenzenc reddish acid yellow I 2 I amino-3-mcthylbenzene reddish yellow l 2 I Laminonaphthulcnc- I -amin0naphthaIenc-fireddish 3 7-disulphonic sulphonic acid yellow acid I22 Z-uminonaphthalenc- I -amino-3-methylbcnzcne 3.6-disulphonic acid I23 I -amino-3-melhyl-6- strongly methoxy-henzene reddish yellow I24 I -amino-3acetylamino reddish benzene yellow I25 II-uminophenyI-urea I 26 I amino-3-hydroxyacclylaminobcnzene I27 I -aminonaphthalene-6- sulphonie acid I 28 l-nminonuphthulcncl-amino-3-acclylamino- 6,8-disulphonic benzene acid I 29 I -amino-Z-methoxynaphthastrongly lene-fi-sulphonic acid reddish yellow I 30 l-uminonaphthalene-6- reddish sulphonic acid yellow I 3 I Z-aminonaphthulencl-aminonaphthaIene-(v yellow 4 8-disulphonic acid sulphonic acid I 32 l-aminonaphthalene-7- sulphonic acid I 3 3 I -amino-2-mclhoxynaphthastrongly lcnc--sulphonic acid reddish yellow I 34 I -mclhylamino-3-methylyellow benzene I35 2-aminonaphthalenel-cthylamino- B-rnethyl- 4.8-disulphonic acid benzene I36 N-methykaniline I37 N-cthylaniline I 38 N-( fihydroxyethyl l-anilinc I 39 Z-aminonaphthalenc- N-bulyl-anilinc yellow 4 B-disulphonic acid I40 Z-aminonaphthalcncaniline reddish 3 6.K-lrisulpi'ionie yellow acid l4l l-amino-B-mclhylhcnzenc I42 3-aminophenyl-urcu I43 l-amino-B-hydroxyucetylaminobenxenc I44 I -amino-Il-acetylamino-hyellowish melhoxybenrene orange I45 l amino-3-aeelylumino-6- reddish melhylhenlene yellow I46 l-amino 3-mcihune-sulphonyluminohcnzenc Continued Example Diazo C oupling Shade on No. component Component cotton I47 3.5-dlmcthoxyanilinc yellowish orange I48 3-methyl-6-mcthox v-anilinc I49 N-melhylmnilinc reddish yellow I50 N-elhyl-aniline lSl N-bulyl-aniline I52 N-( B-hydmxyethyl banilinc 1S3 3-1N-elhylamino)-lolu|:nc 154 2-aminotoluenc I55 I-amino-Zjdimcthylstrongly benzene reddish yellow lSb l -aminoQ-methoxyhcnzene 157 l-amino-3-mcthoxybenzene reddish yellow I58 l-|:thylamino-3-mcthoxybenzene l5) l-aminonaphthalcnc-hsulphonic acid 160 2-aminonaphthalenel-aminonaphthalcnc-7- reddish 3ro 8trisulphonic sulphonic acid yellow acid lbl 2aminonaphthalcnclumin0-3-methylbcnzenc 4.6.X-trisulphunic acid I62 l-amino-3-acctylaminobenzene 163 l 41minunuphthalcnm l -aminu-B-mcthylhcnzcnc yellow 2.4.7-lrisulphonic acid I (14 l -aminonaphthalcnc-6- sulphonic acid I65 4 nitro-4 -zlniinolamino-Smeeiylaminoreddish sIiIl"n:ne-Z.2'-dibenzene yellow sulphunic acid lhb 3-aminophcnyl-urea lh7 l-amino-Il-hydroxyacetylaminohenzenc l (18 N-mcthyl-anilinc I69 N-cthyl-aniline I70 N-hutyl-anilanilinc l 7 l N-(p-hydroxyethyl j-ani|ine I72 l-( N-elhylamino l-3-mcthylbenzene l7] Aniline-2.5-disull-aminonaphthalene-fi-sulphonic acid phonic acid 174 l-aminonnphthalene-7- sulphonic acid I75 l -amino- 3-methylbenzene yellow I76 l-amino-Il-acetylaminobenzene I77 l-amino-Z-methoxy-S-methylreddish benzene yellow l78 l-amino-2.5-dimelhoxybenzene I79 Aniline-2 .d-disulphonic l -amino-2-methoxyreddish acid 5methylbcnzene yellow EXAMPLE I80 65 Parts of the dyestuff of the formula mo s N 2 (prepared by coupling diazotised aminohcnzcnc-4b-disulphonic acid with 2-amino-8- 5 l-hydroxy-2- hydroxynaphthalenc-fi-sulphonic acid and coppering is salted out. filtered off. washed and dried at 3()40C.' The dyestuttdyes cellulose materials by one of the methods described above in very fast ruby shades.

hydroxynaphthalene-3,6-disulphonic acid, and the resultant dyestuff of the formula O3Nu F N: N

r" wan F Cl OH NH-CO-CH Na03 $0 Na No. [)laxo component Coupling component Shade on cotton I l 8 I l -hydroxy 2amino- Z-methylamino-S-hydroxyruby benzenet-sulphonic naphthalene-7-sulphonic acid acid 182 2-elhylamino 5-hydroxy ruby naphthaleneJ-sulphonic acid 18 3 2-( p-hydroxyethylamino ruby S-hydroxynaphthalene-7- sulphonic acid l 84 2amino8-hyd roxynaphthalruby cue-3.6-disulphonic acid H45 l-hydroxy-2 amino- Z-amino-S-hydroxynaphthalruby benzene4,6-disul ene-l .7-disulphonic acid phonic acid l 86 lumino-S-hydroxynaphthalruby ene-3.6-disulphonic acid I37 2-methylamino-S-hydroxy ruby naphthalene-Tmlphonic acid I88 Z-ethylamino-S-hydroxyruby naphthalene-7sulphonic acid l8) Z-lp-hydroxyethylamino ruby S-hydroxynaphthalene-T sulphonic acid 190 l-hydroxy-2-aminol -amino-R-hydroxynaphthviolet benzene-4.6disul alene-3 6-disulphonic phonic acid acid 191 l-amino-8-hydroxynaphthviolet alene-4 6-disulphonic acid I92 l-hyd roxy-lamino l-amino-8-hydroxynaphthviolet benzene-S-sulphonic alene-3,6disulphonic acid acid I93 l-amino 8hydroxynaphthalviolet ene-4,6-disulphonic acid 1'94 l-hydroAy-laminol-amino-8-hyd roxynaphthbluish 4-aeetylamimihenzalene3 fi-disulphonic violet ene-(i-sulphonic acid acid l 95 lhydroxy-Z-nminol-ethoxy-8-hydroxynaphth- 4--.icetylaminobenzalene-3.6-disulphonic cne-fi-sulphonic acid aeid (4-positioned acetylamino group subsequently hydrolysed] I96 l-amino-8-hydroxynaphthblue alenc-ZA-disulphonic acid I97 l41mino8-hydroxynaphthblue alene-Z,4.6-trisulphonic acid I98 lhyd roxy-laminol-amino-B-hydroxynaphthblue S-acetylaminobenalenc-2 4-disulphonic acid renc-l-sulphonic acid (i-positioned acetylamino group hydrolysed) l9) l -amino-lhydroxy-fiblue nitronaphthalene-4- sulphonic acid (ti-positioned nitro group subsequently reduced to -NH,) 200 l-amino-Z-hydroxyl-amino-8-hydroxynaphthblue 6-nitronaphthalcnealone-2.4.6-trisulphonic 4-sulphonic acid acid (6positioncd nitro group subsequently reduced to NH. 201 l-hydroxy-2-amino blue 6acetylaminobenzene-4-sulphonic acid b-positioned acetylamino group hydrolysed] EXAMPLE 202 The procedure is as described in Example 30 but the diazotised reactive group-containing intermediate is coupled in a soda-alkaline medium. instead of with 47 6 parts of the sodium salt of l -bcnzoylamino-8- hydroxynaphthalene-3,fi-disulphonic acid. with 40 parts of the sodium salt of l-acetylamino-K- l-aminobenzene-4-sulphonic acid and 6.9 parts sodium nitrite in 200 parts of water is poured into a mixture of 100 parts of ice and 28 parts by volume of concentrated hydrochloric acid; the reaction mixture is then stirred for one-half hour at ()*I()C and the excess nitrous acid is subsequently removed. The diazo suspension so obtained is admixed at l()C with a cooled and thereby partially crystallised solution of 26.2 parts of the potassium salt of l-aminonaphthalene-S- sulphonic acid in 250 parts of hot water and the strongly acidic coupling mixture is neutralised at l0-20C to pH 4 by the careful addition of a sodium hydroxide solution. The coupling is rapidly completed; the aminoazo dyestuff formed is completely salted out with 100 parts sodium chloride, filtered off with suction, washed and redissolved in 500 parts of water at C and pH 6-7. The aqueous solution is mixed dropwise with parts 2,4,6-trifluoro-5-chloropyrimidine and stirred at 203()C, while continuously neutralising the liberated acid to pH 6-7 by means of a sodium carbonate solution. When the aminoazo dyestuff can no longer be detected. the reactive dyestuff of the formula F N{ N=o s N N I N ing, there is obtained a yellow powder which readily dissolves in water to give a yellow colour and dyes cellulose fibres by one of the dyeing methods described above in the presence of acid-binding agents in yellow shades of very good fastness to wet processing, light and chlorine. Fast yellow dyeings are also obtained on wool and polyamide fibres.

When the procedure described above is followed but, instead of 19.5 parts of the sodium salt of l-aminobenzene-4-sulphonic acid, equivalent amounts of the diazo components stated in the following Table are coupled with l-aminonaphthalene-8-sulphonic acid, then valuable yellow to brown reactive dyestuffs are likewise obtained after acylation with 2,4,6-trifluoro-S-chloropyrimidine.

4-amino-2aicetylamino-aaobenzenei .5 disulphonic acid SO Nu orange-brown reddish brim n -Continued Shade on cellulose Diazo component fibres l l-aniinobenzenc-2.S-disulphonic acid coupled in an acidic medium \iith Lamino-naphthalene-h-sulphonii: acid] N N NH reddish SO NO brown l l-aminobenzene-2.5-disulphonic acid coupled in an acidic medium with the technical mixture of l-aminonaphthalenwf and -7 sulphonic acid) N =N Z violettinted NuOsS brown l-amino-naphlhulene-l5,7-trisulphonic acid coupled in an acidic medium with l-umino-naphthalene-b-sulphonic acid N N 6 H2 reddish brown 0 5 CH 1 amino-naphthalenci ,5 ,b-trisulphonic acid coupled in an acidic medium with l -amino-2 methoxy-5-meth ylhenze ne) EXAMPLE 204 When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g of the dyestuff described in Example I8, I00 g urea, 300 g of water, 500 g of alginate thickening agent g sodium alginate per kilogram thickening agent), l0 g sodium carbonate and 10 g of the sodium salt of 3-nitrobenzenesulphonic acid and which has been made up with water to l kilogram, the fabric is subsequently subjected to an intermediate drying and then steamed in a suitable steaming apparatus at 103 to l 15C for 30 seconds, a bluish red print of good fastness to wet processing, rubbing and light is obtained after rinsing and soaping at the boil.

EXAMPLE 205 A mixture of the solutions of 65.5 parts each of the chromium 2:] complex and the cobalt 2:1 complex of the dyestuff of the formula on no us c n ii==ii each in 400 parts of water, is stirred with 40 parts 2,4,6- trifluoro-5-chloropyrimidine at 3()40C for about 2 hours while maintaining a pH of 6-7. When no more aminoazo dyestuff can be detected by chromatography (Co-complex; blue; Cr-complex; blue-green), the resultant mixture of the two reactive dyestuffs is salted out with potassium chloride. filtered off and dried.

The dyestuff yields on cellulose materials by the pad- F SOQNG \-N FMS-mugdyeing processes or when printed in the presence of ,C ,N acid-binding agents, intense black shades of very good 5 Ho cl fustncss to wet processing and light.

Valuable black dyestuffs are also obtained by proceeding analogously but using a mixture of the chro- M6035 mium 2:l and cobalt 2:] complexes of the following aminoulo dyestuffs- I I I C r 18 filtered off. dissolved warm at pH 6-7 in 3000 parts ouping Dia/u component Coupling component pH of water repreclpftdted m the filtered spluuon I h l 4 h x h 9 by the addition of sodium chloride. After filtering off,

yrox -annnoyr. roxy -ammo-nap I 1 I nilrolicn/cnc thalcnc-3.6-disulphonic drying f p r there obtained a yellow powacid der which IS readily water-soluble and dyes cellulose h\dr m 1 mm 4 9 materials from a long bath at 30C or by the cold batch 4 t i i nitronnplithalcnw7- paddmg process with sodium carbonate as acid blndin g sultthtmis ucid agent in clear yellow shades fast to washing, rubbing and light. EXAMPLE 206 Valuable new reactive dyestuffs are also obtained by A neutral solution Of 53. I5 parts of the disodium salt following the procedure described above, but replacing of the aminoazo dyestuff obtained by coupling diazothe aminoazo dye t ff there used with equivalent tised l-amino-4-nitrobenzene-Z-sulphonic acid with 1- amounts of th aminoazo dyestuffs synthetised from '-Chloro-5-sulphophcnyl)-3-m y -Py -(5) the components stated in the following Table. and subsequent reduction of the nitro group with soln the Table the term hydrolysed"means that an acdium sulphide. in 300 parts of water is admixed with 20 ylamino group contained in the aminoazo dyestuff was parts 2,4 o-trifluoro-S-chloropyrimidine, and the mixsubsequently hydrolysed. while the term reduced" inture is stirred at C for l hour while the liberated dicates that a nitro group contained in the diazo comacid is continuously neutralised to a pH value of 6.0 by ponent is reduced after the coupling to the amino means of a sodium carbonate solution. The precipi- 30 group, whereby the desired aminoazo dyestuff is tated dyestuff of the formula formed.

pH of Example Diazo Azo coupling Shade on No component component medium cellulose 207 l-amino-4-nitro l-(4-sulphophenyl)- 5 6 yellow bcnIenc-Z-sulphonic 3-melhylpyrazoloneacid l-positioned nitro group subsequently reduced) 20% l(4'-sulphophenyl)- 5 6 reddish S-carboxy-pyrazoloneyellow (5) 209 l-(3-sulphophcnyl)- 6 7 yellow B-mcthyl-S-aminopyrazole 210 l-amino-Ii-acctyl- 6 7 aminwbenzenc-fisulphonic acid (B-positioncd acetylamino group subsequently hydrolysed) 21 l l-(p-hydroxycthyl)- 5 e B-meIhyI-pyrazolone- (5] 2l2 2 moles l-uminol mole bis-pyrazol- 5 6 S-acetyl-aminw one from 4,4'-bishenzenc-b-sulhydrazino-dibenzyl phonic acid 2 2-disulphonic (hydrolysed) acid and acetoacetic ethyl ester) ill} I mole l-aminol-(4'-sulphophcnyl)- 5 6 3-acctyl-amino 3-carboxy-pyrazoloncbcnzene6-sul- (5) phonic acid (hydrolysed) 214 Lamina-S-acctyh l-(4'-sulphophcnyl)- 5 6 reddish amino-naphthal- 3-carhoxy-pyra2oloneyellow cne-3.7-disulphonic acid (hydrolysed) 215 l-amino-2-methyl- Z-acetylamino-S- 7 8 orange benzene-4.6-disulnaphlhol-lsuh phonic acid phonic acid (hydrolysed) lib Z-acetylamino-ti- 7 8 red naphthol-fi-sulphonic acid (ludrolyscdl 2 l 7 l-umino-2-mcthy|- l-chloro-Z-acetyl- 7 8 orange henzenc lctmhsulphonic acid amino5-naphthol- 7sulphonic acid (hydrolysed) 

1. A PROCESS OF DYEING WOOL IN A DYE BATH AT A PH IN THE ACID TO NEUTRAL RANGE WHEREIN THE DYESTUFF IS A REACTIVE DYESTUFF OF THE FORMULA:
 2. The process of claim 1 wherein the pH is 6.5 to 8.5.
 3. The process of claim 1 wherein said D contains at least one sulfonic acid group and said group,
 4. The process of claim 1 wherein said reactive dyestuff has the formula:
 5. The process of claim 1 wherein said reactive dyestuff has the formula
 6. A woolen article dyed by the process of claim
 1. 